Fungicidal mixtures

ABSTRACT

Fungicidal compositions comprising an acceptable carrier and/or surface active agent and synergistically effective amounts of  
     (a) at least one azolopyrimidine of formula I  
                 
 
      in which  
     R 1 , R 2 , L 1 , L 2  and L 3  have the meaning given in claim 1; and  
     (b) at least one fungicidal active ingredient selected from benomyl, carboxin, captan, chlorothalonil, copper oxychloride, cyprodinil, dimethomorph, dithianon, dodine, famoxadone, fenhexamid, fenpiclonil, fenpropimorph, fluazinam, mancozeb, metalaxyl, pyrimethanil, quinoxifen, sulfur, triforine, vinclozolin, a fungicidal triazole derivative, and a synthetic strobilurine derivative. The invention also provides a method of controlling the growth of phytopathogenic fungi at a locus by applying synergistically effective amounts of at least one azolopyrimidine of formula I and at least one fungicidal active ingredient (b) to the locus.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to a fungicidal compositioncomprising a fungicidally acceptable carrier and/or surface active agentand synergistically effective amounts of

[0002] (a) at least one azolopyrimidine of formula I

[0003]  in which

[0004] R¹ represents a C₁₋₆ alkyl, C₃₋₆ alkenyl or C₁₋₆ haloalkyl group,or

[0005] R² represents a hydrogen atom or a C₁₋₆ alkyl group, or

[0006] R¹ and R² taken together represent a C₁₋₆ alkylene group,

[0007] L¹ represents a halogen atom;

[0008] L² and L³ each independently represent a hydrogen or a halogenatom; and

[0009] and at least one fungicidal active ingredient selected from thefollowing classes (A), (B) and (C):

[0010] (A) a compound selected from the group consisting of benomyl,carboxin, captan, chlorothalonil, copper oxychloride, cyprodinil,dimethomorph, dithianon, dodine, famoxadone, fenpiclonil, fenpropimorph,fluazinam, mancozeb, metalaxyl, pyrimethanil, quinoxifen, sulfur,triforine and vinclozolin;

[0011] (B) a fungicidal triazole derivative; and

[0012] (C) a synthetic strobilurine derivative.

[0013] The fungicidal compounds of formula I to be used according to thepresent invention are known from U.S. patent U.S. Pat. No. 5,593,996.The compounds of the classes (A) and (B) are known from “The PesticideManual”, 11^(th) edition (1997), Editor Clive Tomlin. Fenhexamid isknown from AGROW No. 287, p. 21. The synthetic strobilurines are known,for example, from WO 92/08703, EP 0 253 213 and EP 0 398 692.

[0014] However, none of the above mentioned prior art references teachesa combination of compounds of formula I with any of the fungicidalactive ingredients selected from the classes (A), (B) and (C) asdescribed above, nor that such mixtures show synergistic effects and canadvantageously be used for controlling diseases such as wheat powderymildew, barley powdery mildew, wheat leaf rust, barley net blotch andwheat Septoria leaf blotch, Botrytis diseases and others.

[0015] Surprisingly, when compounds of formula I were tank mixed withcompounds from classes (A), (B) and (C) and used in greenhouse and fieldtrials, a synergistic increases in activity were observed, compared tothe activity expected based on the activities of the individual activeingredients.

[0016] A mixture of fungicides shows synergistic effect if thefungicidal activity of the mixture is larger than the sum of activitiesof the separately applied compounds. The expected fungicidal activityfor a given mixture of two fungicides can also be calculated as follows(See Colby, S. R., “Calculating synergistic and antagonistic response ofherbicide combinations”, Weeds 15, pp 20-22 (1967):

EE=x+y−xy/100

[0017] wherein

[0018] x is the efficacy in % compared with an untreated control upontreatment with a fungicidal active ingredient A at a dose rate a;

[0019] y is the efficacy in % compared with an untreated control upontreatment with a fungicidal active ingredient B at a dose rate b;

[0020] EE is the expected efficacy with a combination of fungicidalactive ingredients A and B at a dose of a+b, respectively.

[0021] If the actual efficacy (E) exceeds the expected (calculated) one(EE), the mixture displays a synergistic effect.

SUMMARY OF THE INVENTION

[0022] The present invention includes a fungicidal compositioncomprising an acceptable carrier and/or surface active agent andsynergistically effective amounts of at least one compound of formula I,and at least one fungicidal active ingredient selected from thefollowing classes (A), (B) and (C):

[0023] (A) a compound selected from the group consisting of benomyl,carboxin, captan, chlorothalonil, copper oxychloride, cyprodinil,dimethomorph, dithianon, dodine, famoxadone, fenpiclonil, fenpropimorph,fluazinam, mancozeb, metalaxyl, pyrimethanil, quinoxifen, sulfur,triforine and vinclozolin;

[0024] (B) a fungicidal triazole derivative; and

[0025] (C) a synthetic strobilurine derivative.

[0026] The present invention also includes a method of controlling thegrowth of phytopathogenic fungi at a locus which comprises applyingsynergistically effective amounts of at least one azolopyrimidine offormula I and at least one fungicidally active ingredient selected fromclasses (A), (B) and (C) defined above to the locus.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Preferred compounds of formula I are those wherein

[0028] R¹ and R² together with the interjacent nitrogen atom represent a4-methylpiperidine ring, or wherein

[0029] R¹ represents a C₁₋₆ alkyl, in particular an isopropyl group, aC₁₋₆ haloalkyl, in particular a 2,2,2-trifluoroethyl or a1,1,1-trifluoroprop-2-yl group, or a C₃₋₈ cycloalkyl group, inparticular a cyclopentyl or cyclohexyl group and R² represents ahydrogen atom, and/or

[0030] wherein L¹ represents a fluorine or chlorine atom and L² and L³each independently represent a hydrogen atom or a fluorine atom, inparticular

[0031] wherein L¹ represents fluorine, L² represents hydrogen and L³represents chlorine or wherein L¹ through L³ represent fluorine.

[0032] Particularly preferred are the following azolopyrimidines:

[0033]5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperid-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidinecoded Azoloyrimidine A,5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2,2,2-trifluoroethylamino)-[1,2,4]triazolo[1,5-a]pyrimidinecoded Azoloyrimidine B and5-chloro-6-(2,4,6-trifluorophenyl)-7-(1,1,1-trifluoroprop-2-ylamino)-[1,2,4]triazolo[1,5-a]pyrimidinecoded Azoloyrimidine C. Azolopyrimidine C due to the chirality of its1,1,1-trifluoroprop-2-yl group may be applied as a racemic mixture or inthe form of an enantiomeric enriched compound, in particular as(S)-enantiomer coded (S)-Azolopyrimidine C.

[0034] Preferred triazole derivatives in the practice of this inventionare the compounds of formula II,

[0035] wherein

[0036] L represents a linking group selected from the groups (a), (b),(c) and (d)

[0037]  in which

[0038] X¹ represents an alkyl or an optionally substituted phenyl group;

[0039] X² and X³ each independently represent a hydrogen atom or analkyl group;

[0040] X⁴ represents an alkyl or cyclopropylalkyl group;

[0041] q is 1 or 2; and

[0042] n is 0 or 2.

[0043] Particularly preferred are the triazoles selected from the groupconsisting of cyproconazole, epoxiconazole, metconazole, propiconazoleand tebuconazole.

[0044] Preferred strobilurine derivatives in the practice of thisinvention are the compounds of formula III,

[0045] wherein

[0046] A represents N or CH;

[0047] B represents a —O—, —OCH₂—, a —CH₂O—, a pyrimid-4,6-dioxydiylgroup or a group of formula

[0048] R³ represents a C₁₋₄ alkyl group;

[0049] R⁴ represents a C₁₋₆ alkoxy or a C₁₋₆ alkylamino group;

[0050] R⁵ represents a hydrogen or halogen atom or a cyano, a C₁₋₄ alkylor a C₁₋₄ haloalkyl group; and

[0051] m is 0, 1 or 2;

[0052] in particular azoxystrobin, kresoxim methyl, CGA-279202 (AGROW279, p.17 1998) or SSF126 (Pesticide Manual, loc. cit., page 1114)

[0053] Preferred compositions of this invention comprise the followingconstituents:

[0054] a carrier agent;

[0055] at least one azolopyrimidine of formula I,

[0056] at least one compound selected from the classes (A), (B) and (C)as defined above;

[0057] optionally an adjuvant selected from the group consisting ofpolyalkoxylated alcohols, triglycerides and amines, in particularSynperonic 91-6, which is commercially available from ICI Surfactants;

[0058] optionally a foam breaking agent, in particular a mixture ofperfluoroalkyphosphonic acids and/or perfluoroalkylphosphinic acids, inparticular Defoamer SF or Fluowett PL, which are commercially availablefrom Clariant GmbH.

[0059] The compound of formula I and the compound selected from theclasses (A), (B) and (C) as defined above are to be applied together, insynergistically effective amounts. These synergistic mixtures exhibit anextraordinary efficacy against a broad range of phytopathogenic fungi,in particular against fungi from the classes ascomycetes,basidiomycetes, oomycetes and deuteromycetes. Therefore, they can beapplied advantageously against a broad range of diseases in differentcrops. They may be applied as leaf, stem, root, into-water, seeddressing, nursery box or soil fungicides.

[0060] The composition according to the invention may be preferablyapplied for controlling phytopathogenic fungi of the genera: Achlya,Alternaria, Balansia, Bipolaris, Blumeria (Erysiphe), Cercospora,Cochliobolus, Curvularia, Cylindrocladium, Drechslera, Entyloma,Fusarium, Gaeumannomyces, Gerlachia, Gibberella, Guignardia,Leptosphaeria, Magnaporthe, Mucor, Mycosphaerella, Myrothecium,Nigrospora, Peronospora, Phoma, Pseudoperonospora, Pseudocercosporella,Phytophthora, Puccinia, Pyricularia, Pythium, Rhizoctonia, Rhizopus,Sarocladium, Sclerophthora, Sclerotium, Septoria, Tilletia, Uncinula,Ustilago, Ustilaginoidea, and Venturia, in particular the speciesBlumeria graminis f. sp. tritici, Botrytis cinerea, Septoria triticiErysiphe cichoracearum and Puccinia recondita.

[0061] The compositions according to the invention are preferablyapplied for controlling the above phytopathogenic fungi onmonocotylydoneous plants, such as barley and wheat, rice and turfgrases, or fruit crops such as pomefruits, stonefruits and vines, aswell as all kinds of vegetables, oil and oil seed crops, andornamentals.

[0062] The application rate of the compound of formula I according tothis invention is suitably in the range of 1 to 2000 grams of activeingredient (g a.i.) per hectare, with rates between 20-500 g a.i./haoften achieving satisfactory control. The optimal rate for a specificapplication will depend on the crop(s) under cultivation and thepredominant species of infesting fungi, and readily may be determined byestablished biological tests known to those skilled in the art.

[0063] In general, the preferred application rate of the compounds offormula I is in the approximate range of 10 to 500 g a.i./ha, morepreferably 20-300 g a.i./ha.

[0064] The optimal rate for the compounds of classes (A), (B) and (C),will, however, depend on the crop(s) under cultivation and the level ofinfestation by the fungus, and can readily be determined by establishedbiological tests.

[0065] The approximate ratio (by weight) of the compound of formula I tothe fungicidal active ingredient of the classes (A), (B) and (C) issuitably from 1:100 to 100:1. The preferred ratio formula I: (A), (B) or(C) may vary, e.g., from about 1:50 to about 50:1, in particular fromabout 1:4 to about 4:1, most preferably from 1:1.5 to 1.5:1.

[0066] The active compounds can be co-formulated together in a suitableratio according to the present invention, together with carriers and/oradditives known in the art.

[0067] A method of making such a composition is also provided whichcomprises bringing the compound of formula I and the fungicidal activeingredient selected from the classes (A), (B) and (C) as defined aboveinto association with at least one carrier. It is also envisaged thatdifferent isomers or mixtures of isomers of formula I and/or thefungicidal active ingredient selected from the classes (A), (B) and (C)may have different levels or spectra of activity and thus compositionsmay comprise individual isomers or mixtures of isomers.

[0068] A composition according to the invention preferably contains from0.1% to 99.9%, preferably 0.2 to 80% by weight (w/w) of activeingredients.

[0069] A carrier in a composition according to the invention may be anymaterial with which the active ingredients may be formulated tofacilitate application to the locus to be treated (which may, forexample, be a plant, seed, foliage, soil, or into the water where theplant grow or to the roots), or to facilitate storage, transport orhandling. A carrier may be a solid or a liquid, including material whichis normally a gas but which has been compressed to form a liquid.

[0070] The compositions may be manufactured into, e.g., emulsion oremulsifiable concentrates, solutions, oil in water emulsions, wettablepowders, soluble powders, suspension concentrates, dusts, granules,aerosols, water dispersible granules, tablets, micro-capsules, gels andother formulation types by well-established procedures. These proceduresmay include intensive mixing and/or milling of the active ingredientswith other substances, such as fillers, solvents, solid carriers,surface active compounds (surfactants), and, optionally solid and/orliquid auxilaries and/or adjuvants. The form of application such asspraying, atomizing, dispersing or pouring may be chosen like thecompositions according to the desired objectives and the givencircumstances.

[0071] Solvents used in the composition of this invention may bearomatic hydrocarbons, e.g. Solvesso® 200, substituted naphthalenes,phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatichydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols aswell as their ethers and esters, e.g. ethanol, ethyleneglycol mono- anddimethyl ether, ketones such as cyclohexanone, strongly polar solventssuch as N-methyl-2-pyrrolidone, or γ-butyrolactone, higher alkylpyrrolidones, e.g. n-octylpyrrolidone or cyclohexylpyrrolidone,epoxidized plant oil esters, e.g. methylated coconut or soybean oilester and water. Mixtures of different solvents may be suitable.

[0072] Solid carriers used in the composition of this invention whichmay be used for dusts, wettable powders, water dispersible granules, orgranules, may be mineral fillers, such as calcite, talc, kaolin,montmorillonite or attapulgite or others. The physical properties may beimproved by addition of highly dispersed silica gel or polymers.Carriers for granules may be porous material, e.g., pumice, kaolin,sepiolite, bentonite; non-sorptive carriers may be calcite or sand orothers. Additionally, a multitude of pre-granulated inorganic or organicmaterials may be used, such as dolomite or crushed plant residues.

[0073] Pesticidal compositions are often formulated and transported in aconcentrated form which is subsequently diluted by the user beforeapplication. The presence of small amounts of a carrier which is asurfactant facilitates this process of dilution. Thus, preferably atleast one carrier in a composition according to the invention is asurfactant. For example, the composition may contain two or morecarriers, at least one of which is a surfactant.

[0074] Surfactants may be nonionic, anionic, cationic or zwitterionicsubstances with good dispersing, emulsifying and wetting properties,depending on the nature of the active ingredients to be formulated.Surfactants may also include mixtures of individual surfactants.

[0075] Wettable powders in this invention suitably may contain about 5to 90% w/w of active ingredient and, in addition to solid inert carrier,about 3 to 10% w/w of dispersing and wetting agents and, wherenecessary, 0 to 10% w/w of stabilizer(s) and/or other additives such aspenetrants or stickers. Dusts may be formulated as a dust concentratehaving a similar composition to that of a wettable powder but without adispersant, and may be diluted in the field with further solid carrierto give a composition containing about 0.5 to 10% w/w of activeingredient. Water dispersible granules and granules may have a sizeapproximately between 0.15 mm and 2.0 mm, and may be manufactured by avariety of techniques known in the art. These granules suitably willcontain about 0.5 to 90% w/w active ingredient and 0 to 20% w/w ofadditives such as stabilizer, surfactants, slow release modifiers andbinding agents. Emulsifiable concentrates suitably may contain, inaddition to a solvent or a mixture of solvents, approximately 1 to 80%w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v ofother additives, such as stabilizers, penetrants and corrosioninhibitors. Suspension concentrates may be milled so as to obtain astable, non-sedimenting flowable product and suitably contain about 5 to75% w/v active ingredient, and 0.5 to 15% w/v of dispersing agents, 0.1to 10% w/v of suspending agents such as protective colloids andthixotropic agents, 0 to 10% w/v of other additives such as defoamers,corrosion inhibitors, stabilizers, penetrants and stickers, and water oran organic liquid in which the active ingredient is substantiallyinsoluble; certain organic solids or inorganic salts may be presentdissolved in the formulation to assist in preventing sedimentation andcrystalization or as antifreeze agents.

[0076] Aqueous dispersions and emulsions, for example compositionsobtained by diluting the formulated product according to the inventionwith water, also lie within the scope of the invention.

[0077] The invention also encompasses the use of a carrier which willprovide slow release of the pesticidal compounds into the environment ofa plant which is to be protected, to extend the duration of theprotective activity of the composition.

[0078] The biological activity of the active ingredients may beincreased by including an adjuvant in the formulation or a spraydilution. An adjuvant is defined here as a substance which can increasethe biological activity of an active ingredient but is not itselfsignificantly biologically active. The adjuvant can either be includedin the formulation as a coformulant or carrier, or can be added to thespray tank together with the formulation containing the activeingredient.

[0079] As a commodity, the compositions may preferably be in aconcentrated form whereas the end user generally employs dilutedcompositions. The compositions may be diluted to a concentration down toabout 0.001% of active ingredient. The doses preferably are in theapproximate range from 0.01 to 10 kg a.i./ha.

[0080] Examples of formulations useful in the practice of the inventionare: SC-I 1 active ingredient Azolopyrimidine C 100.0 g Dispersing agentMorwet D425¹⁾ 25.0 g Dispersing agent Pluronic ® PE 10500²⁾ 5.0 gAntifoaming agent Rhodorsil ® 426R³⁾ 1.5 g Dispersing agent Rhodopol ®23³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agentProxel ® GXL⁴⁾ 1.0 g Water to 1000 ml SC-I 2 active ingredientAzolopyrimidine C 100.0 g Dispersing agent Soprophor ® FL³⁾ 30.0 gAntifoaming agent Rhodorsil ® 426R³⁾ 1.5 g Dispersing agent Rhodopol ®23³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agentProxe I ® GXL⁴⁾ 1.0 g Water to 1000 ml SC-A/B/C active ingredientselected from classes (A), (B), (C) 200.0 g Dispersing agent Soprophor ®FL³⁾ 25.0 g Antifoaming agent Rhodorsil ® 426R³⁾ 1.5 g Dispersing agentRhodopol ® 23³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 gBiocidal agent Proxel ® GXL⁴⁾ 1.0 g Water to 1000 ml SC-I + A/B/C activeingredient Azolopyrimidine C 60.0 g active ingredient selected fromclasses (A), (B) and 120.0 g (C) Dispersing agent Soprophor ® FL³⁾ 25.0g Antifoaming agent Rhodorsil ® 426R³⁾ 1.5 g Dispersing agent Rhodopol ®23³⁾ 2.0 g Antifreezing agent Propylene glycol 80.0 g Biocidal agentProxel ® GXL ⁴⁾ 1.0 g Water to 1000 ml DC-I 1 active ingredientAzolopyrimidine A 100.0 g Wetting agent Pluronic ® PE6400²⁾ 50.0 gDispersing agent Lutensol ® TO 12²⁾ 50.0 g Solvent benzyl alcohol to1000 ml

[0081] The formulation SC-A/B/C,comprising a compound selected from theclasses (A), (B) and (C), may be mixed with any of the otherformulations SC-I 1, SC-I 2, SC-I 3, or DC-I which comprise theAzolopyrimidine C to produce a composition of this invention.

[0082] In a preferred embodiment of the invention, each activeingredient is added to a tank mix in a separate formulation, to form acomposition of this invention.

[0083] The present invention also relates to a kit for the preparationof a spray mixture consisting of two separate units:

[0084] (i) a unit which comprises at least one azolopyrimidine offormula I, in particular one or more compounds selected from theAzolopyrimidines A, B or C, conventional carriers and optionallyadjuvants;

[0085] (ii) a unit which comprises at least one active ingredientselected from the classes (A), (B) and (C), preferably one or morecompounds selected from the group consisting of carboxin, fluazinam,quinoxifen, metalaxyl, famoxadone, metconazole, epoxiconazole,propiconazole, azoxystrobin or kresoxim methyl conventional carriers andoptionally adjuvants.

[0086] In a preferred embodiment, the kit includes two bottles withdispensing means which allow the easy and correct addition of the activeingredients to the tank mix.

[0087] A composition according to the invention preferably contains fromabout 0.5% to 95% by weight of active ingredients.

[0088] The compositions of this invention may be diluted down to aconcentration of about 0.0001% of active ingredients.

[0089] The compositions of this invention can be applied to the plantsor their environment simultaneously with or in succession with otheractive substances. These other active substances can be eitherfertilizers, agents which donate trace elements, or other preparationswhich influence plant growth. However, they can also be otherfungicides, selective herbicides, insecticides, bactericides,nematicides, algicides, molluscidides, rodenticides, virucides,compounds inducing resistance into plants, biological control agentssuch as viruses, bacteria, nematodes, fungi and other microorganisms,repellents of birds and animals, and plant growth regulators, ormixtures of several of these preparations, if appropriate together withother carrier substances conventionally used in the art of formulation,surfactants or other additives which promote application.

[0090] Examples of insecticidal compounds useful in this invention arealpha-cypermethrin, benfuracarb, BPMC, buprofezine, carbosulfan, cartap,chlorfenvinphos, chlorpyrifos-methyl, cycloprothrin, cypermethrin,esfenvalerate, ethofenprox, fenpropathrin, flucythrinate, flufenoxuron,hydramethylnon, imidacloprid, isoxathion, MEP, MPP, nitenpyram, PAP,permethrin, propaphos, pymetrozine, silafluofen, tebufenozide,teflubenzuron, temephos, terbufos, tetrachlorvinphos and triazamate.

[0091] Examples of biological control agents useful in this inventionare: Bacillus thuringiensis, Verticillium lecanii, Autographicacalifornica NPV, Beauvaria bassiana, Ampelomyces quisqualis, Bacilissubtilis, Pseudomonas fluorescens, Steptomyces griseoviridis andTrichoderma harzianum.

[0092] Examples of chemical agents that induce systemic acquiredresistance in plants are: isonicotinic acid or derivatives thereof,2,2-dichloro-3,3-dimethylcyclopropylcarboxylic acid and BION.

[0093] The present invention is of wide applicability in the protectionof crops, trees, residential and ornamental plants against fungalattack. Preferred crops are cereals, such as wheat and barley, rice,vines, and apples. The duration of the protection is normally dependenton the individual compound selected, and also a variety of externalfactors, such as climate, the impact of which may be mitigated by theuse of a suitable formulation.

[0094] The following examples further illustrate the present invention.It should be understood, however, that the invention is not limitedsolely to the particular examples given below.

EXAMPLES General Methods

[0095] The trials are carried out under greenhouse (Examples 1 to 32) orfield conditions (Examples 33 to 40) in residual or curativeapplications. The fungicides are applied in single treatments, or in acombination comprising an azolopyrimidine of formula I and a compoundselected from the classes (A), (B) and (C) as defined above. Thecompounds are applied in form of an aqueous spray mix obtained from aconcentrated formulation or the technical material.

[0096] I. Cereals and Dicots—Greenhouse

[0097] 1. Seed is planted in 6 cm diameter plastic pots and maintainedin the greenhouse.

[0098] 2. When the primary leaf is fully expanded in the case of cerealsor several leaves are present in the case of dicots, formulated testcompounds are sprayed with a three nozzle overhead fungicide sprayer tonear run-off. Alternatively, a single nozzle overhead track sprayer isused for application of the compounds to cereals at a rate of 200 l/ha.Plants are then allowed to air-dry.

[0099] 3. Inoculation precedes treatment in the case of curativeevaluations and follows treatment in case of residual evaluations. Forinoculation of powdery mildew disease, plants are set up on greenhousebenches with bottom watering mats and inoculated by dusting them withconidia from infected plants. Between inoculation and treatment forcurative evaluations and between treatment and inoculation for residualevaluations, plants are maintained in the greenhouse with bottomwatering.

[0100] For inoculation of non-powdery mildew diseases, an aqueous sporesuspension of the pathogen is applied to the plant and the plants arekept 1-2 days in a moist infection chamber before being returned to thegreenhouse where they are maintained by bottom watering.

[0101] 4. Disease on the foliage as percent leaf area with diseasesymptoms/signs is evaluated about 7 days after inoculation. In the caseof wheat, the tips and bases of the leaves are excluded from theevaluation.${\% \quad {disease}\quad {control}} = {100 - {\frac{\% \quad {disease}\quad {in}\quad {treated}\quad {plants}}{\% \quad {disease}\quad {in}\quad {untreated}\quad {plants}} \times 100\%}}$

[0102] Formulation, Reference Compounds and Controls:

[0103] 1. Technical compounds are formulated in a solvent/surfactantsystem consisting of 5% acetone and 0.05% Tween 20 in deionized water.Compounds are dissolved in acetone prior to addition of the water; theTween 20 can be added through either the acetone or the water. Dilutionsare made using the solvent/surfactant system. Formulated compounds areprepared using deionized water.

[0104] 2. Two kinds of controls are included: Plants treated with thesolvent/surfactant solution and inoculated (Solvent Blank). Untreatedplants which are inoculated (Inoculated Control).

[0105] For the field study formulated Azolopyrimidine A, B or C andformulated compounds from the classes (A), (B) and (C) were used.

[0106] Evaluation of the Disease:

[0107] Assessments of the diseases took place at the indicated day afterthe application of the compounds. Per cent infected leaf area infectedwas evaluated. The efficacy of the compounds/compounds mixtures tocontrol the diseases was calculated by using the formula given aboveunder item 4:

[0108] II. Apple Fruit Botrytis

[0109] 1. Apples (Malus X domestica Borkh.) variety Golden Delicious aredisinfected by washing them briefly in 70% ethanol. After drying theapples are marked with four short equal-distant lines indicating thepositions to be wounded.

[0110] 2. Corresponding with the marks, four holes are poked around theapple equator with a pipette tip. 10 μl of the treatment solution arepipetted into each hole.

[0111] 3. Three hours after application, 10 μl of a conidial suspensionof Botrytis cinerea are pipetted into each. For incubation, thetreated/inoculated apples are set up for five days.

[0112] 4. Disease occurs as rotten apple tissue surrounding theinoculated wounds. The diameter of the rotten zone around each wound ismeasured.

[0113] Formulation, Reference Compounds and Controls:

[0114] 1. Technical compounds are formulated in a solvent systemconsisting of 5% acetone and 0.05% Tween 20 in deionized water.Compounds are dissolved in acetone prior to dilution with water.Formulated compounds are prepared using deionized water.

[0115] 2. Three kinds of controls are included:

[0116] Apples treated with the solvent solution and inoculated (SolventBlank).

[0117] Untreated apples which are inoculated (Inoculated Control).

[0118] Untreated apples which are not inoculated (Uninoculated Control).

[0119] Evaluation of the Disease:

[0120] Assessments of the diseases took place at the indicated day afterthe application of the compounds. Per cent infected leaf area infectedwas evaluated. The efficacy of the compounds/compounds mixtures tocontrol the diseases was calculated by using the formula:${\% \quad {disease}\quad {control}} = {100 - {\frac{{mean}\quad {of}\quad {diameters}\quad {on}\quad {treated}\quad {apples}}{{mean}\quad {of}\quad {diameters}\quad {on}\quad {untreated}\quad {apples}} \times 100\%}}$

[0121] Determination of Synergy:

[0122] Synergy was calculated using the % disease control values ofspecific treatments for the two COLBY formula given hereinabove

[0123] III. Field Tests

[0124] The compounds are applied according to good agricultural practicein the form of an aqueous spray mix obtained from a concentratedformulation or the technical material at a rate of 400 l/ha. The diseasecontrol is evaluated according to the formula given for the greenhousetests.

[0125] A Greenhouse Tests

Example 1

[0126] Fungicidal efficacy of the mixture of AzolopyrimidineA+fenpropimorph (3 day residual) against Leptosphaeria nodorum on wheatThe tank mix was obtained from technical material of Azolopyrimidine Aand an EC formulation containing 750 g fenpropimorph per liter. Theobserved and expected efficacies with different rates are given in TableI: TABLE I dose rate (ppm) Observed Expected Azolopyrimidine Afenpropimorph Efficacy Efficacy 100 0 40 — 10 0 35 — 0 5 15 — 0 0.5 19 —100 5 71 49 100 0.5 80 51 10 5 55 45 10 0.5 50 47

Example 2

[0127] Fungicidal efficacy of the mixture of AzolopyrimidineA+tebuconazole (3 day residual) against Leptosphaeria nodorum on wheatThe tank mix was obtained from technical material of Azolopyrimidine Aand an EC formulation containing 250 g tebuconazole per liter. Theobserved and expected efficacies with different rates are given in TableII: TABLE I dose rate (ppm) Observed Expected Azolopyrimidine Atebuconazole Efficacy Efficacy 100 0 40 — 0 0.2 19 — 0 0.02 25 — 100 0.288 51 100 0.02 87 55

Example 3

[0128] Fungicidal efficacy of the mixture of AzolopyrimidineA+tebuconazole (2 day residual) against Blumeria graminis on wheat Thetank mix was obtained from technical material of Azolopyrimidine A andan EC formulation containing 250 g tebuconazole per liter. The observedexpected efficacies with different rates are given in Table III: TABLE Idose rate (ppm) Observed Expected Azolopyrimidine A tebuconazoleEfficacy Efficacy 10 0 14 — 0 0.2 9 — 0 0.02 2 — 10 0.2 52 22 10 0.02 3316

Example 4

[0129] Fungicidal efficacy of the mixture of AzolopyrimidineA+vinclozolin (3 day residual) against Botrytis cinerea on apple fruitsThe tank mix was obtained from technical material of Azolopyrimidine Aand a WG formulation containing 500 g vinclozolin per kg. The observedand expected efficacies with different rates are given in Table IV:TABLE I dose rate (ppm) Observed Expected Azolopyrimidine A vinclozolinEfficacy Efficacy 10 0 33 — 1 0 0 — 0 10 8 — 10 10 54 38 1 10 31  8

Example 5

[0130] Fungicidal efficacy of the mixture of AzolopyrimidineA+cyprodinil (3 day residual) against Botrytis cinerea on apple fruitsThe tank mix was obtained from technical material of Azolopyrimidine Aand a WG formulation containing 750 g cyprodinil per kg. The observedand expected efficacies with different rates are given in Table V: TABLEV dose rate (ppm) Observed Expected Azolopyrimidine A cyprodinilEfficacy Efficacy 10 0 33 — 1 0 0 — 0 1 46 — 0 0.1 2 — 10 1 66 64 10 0.161 34 1 0.1 3  2

Example 6

[0131] Fungicidal efficacy of the mixture of Azolopyrimidine A+benomyl(3 day residual) against Botrytis cinerea on apple fruits The tank mixwas obtained from technical material of Azolopyrimidine A and a WPformulation containing 500 g benomyl per kg. The observed and expectedefficacies with different rates are given in Table VI: TABLE VI doserate (ppm) Observed Expected Azolopyrimidine A benomyl Efficacy Efficacy10 0 0 — 1 0 0 — 0 10 13 — 0 1 0 — 10 10 87 35 10 1 38 25 1 10 35 13 1 115  0

Example 7

[0132] Fungicidal efficacy of the mixture of AzolopyrimidineA+vinclozolin (3 day residual) against Botrytis cinerea on apple fruitsThe tank mix was obtained from technical material of Azolopyrimidine Aand a WG formulation containing 500 g vinclozolin per kg. The observedand expected efficacies with different rates are given in Table VII:TABLE VII dose rate (ppm) Observed Expected Azolopyrimidine AVinclozolin Efficacy Efficacy 10 0 25 — 1 0 0 — 0 10 17 — 0 1 0 — 10 1057 38 1 1 4  0

Example 8

[0133] Fungicidal efficacy of the mixture of AzolopyrimidineC+metconazole (1 day residual) against Rhynchosporium secalis on barleyThe tank mix was obtained from technical materials of Azolopyrimidine Cand metconazole. The observed and expected efficacies are given in TableVIII: TABLE VIII dose rate (ppm) Observed Expected Azolopyrimidine Cmetconazole Efficacy Efficacy 100 0 15 — 0 100 87 — 100 100 100 89

Example 9

[0134] Fungicidal efficacy of the mixture of AzolopyrimidineC+metconazole (1 day residual) against Septoria tritici on wheat Thetank mix was obtained from a SC formulation containing 100 gAzoplopyrimidine C per liter and an EC containing 100 g metconazole perliter. The observed and expected efficacies with different rates aregiven in Table IX: TABLE IX dose rate (ppm) Observed ExpectedAzolopyrimidine C metconazole Efficacy Efficacy 40 0 91 — 25 0 68 — 8 00 — 5 0 0 — 2 0 0 — 0 25 0 — 0 10 0 — 0 8 0 — 0 5 0 — 0 2 0 — 40 10 9291  25 25 89 68  8 2 11 0 5 5 16 0 2 8 28 0

Example 10

[0135] Fungicidal efficacy of the mixture of AzolopyrimidineC+metconazole (1 day residual) against Pyrenophora teres on barley Thetank mix was obtained from a SC formulation containing 100 gAzolopyrimidine C per liter and an EC containing 100 g metconazole perliter. The observed and expected efficacies with different rates aregiven in Table X: TABLE XI dose rate (ppm) Observed ExpectedAzolopyrimidine C Metconazole Efficacy Efficacy 125 0 0 — 50 0 0 — 40 00 — 25 0 0 — 10 0 0 — 0 200 73 — 0 125 68 — 0 40 34 — 0 25 9 — 0 10 4 —125 125 69 68 50 200 82 73 25 25 46  9 40 10 9  4 10 40 51 34

Example 11

[0136] Fungicidal efficacy of the mixture of AzolopyrimidineC+metconazole (1 day residual) against Puccinia recondita on wheat Thetank mix was obtained from from a SC formulation containing 100 gAzolopyrimidine C per liter and an EC containing 100 g metconazole perliter. The observed and expected efficacies with different rates aregiven in Table XI: TABLE XI dose rate (ppm) Observed ExpectedAzolopyrimidine C metconazole Efficacy Efficacy 200 0 35 — 125 0 20 — 400 10 — 25 0 5 — 10 0 3 — 8 0 1 — 2 0 2 — 0 125 97 — 0 50 72 — 0 40 31 —0 25 14 — 0 10 8 — 0 8 0 — 0 2 0 — 200 50 86 82 125 125 99 98 40 10 2517 25 25 22 18 10 40 70 33 8 2 1  1 2 8 8  2

Example 12

[0137] Fungicidal efficacy of the mixture of Azolopyrimidine C+kresoximmethyl (1 day curative) against Puccinia recondita on wheat Plantssprayed twice, once with each compound. The tank mixes were obtainedfrom a SC formulation containing 100 g Azolopyrimidine C per liter and aWG containing 500 g kresoxim methyl per kg. The observed and expectedefficacies with different rates are given in Table XII: TABLE XII doserate (g/ha) Observed Expected (S)-Azolopyrimidine C kresoxim methylEfficacy Efficacy 400 0 99 — 200 0 97 — 100 0 79 — 50 0 66 — 25 0 25 — 0400 5 — 0 200 1 — 0 100 0 — 0 50 1 — 0 25 0 — 400 400 99 99 200 200 9497 100 100 86 79 50 50 84 66 25 25 29 25

Example 13

[0138] Fungicidal efficacy of the mixture of Azolopyrimidine C+carboxin(1 day residual) against Puccinia recondita on wheat The tank mix wasobtained from technical material of Azolopyrimidine C and WP formulationcontaining 750 g carboxin per kg. The observed and expected efficacieswith different rates are given in Table XIII: TABLE XIII dose rate (ppm)Observed Expected Azolopyrimidine C carboxin Efficacy Efficacy 4 0 100 —1 0 71 — 0.25 0 41 — 0.06 0 8 — 0 4 4 — 0 1 0 — 0 0.25 0 — 0 0.06 0 — 44 100 100  1 1 89 71 0.25 0.25 66 49 0.06 0.06 59  8

Example 14

[0139] Fungicidal efficacy of the mixture of Azolopyrimidine C+fluazinam(1 day residual) against Puccinia recondita on wheat The tank mix wasobtained from technical material of Azolopyrimidine C and a SCformulation containing 500 g fluazinam per liter. The observed andexpected efficacies with different rates are given in Table XIV: TABLEXIV dose rate (ppm) Observed Expected Azolopyrimidine C fluazinamEfficacy Efficacy 4 0 100 — 1 0 71 — 0.06 0 8 — 0 4 17 — 0 1 4 — 0 0.060 — 4 4 100 100  1 1 92 72 0.06 0.06 24  8

Example 15

[0140] Fungicidal efficacy of the mixture of AzolopyrimidineC+quinoxyfen (1 day residual) against Puccinia recondita on wheat Thetank mix was obtained from technical material of Azolopyrimidine C andquinoxyfen. The observed and expected efficacies with different ratesare given in Table XV: TABLE XV dose rate (ppm) Observed ExpectedAzolopyrimidine C quinoxyfen Efficacy Efficacy 4 0 100 — 1 0 71 — 0.25 049 — 0.06 0 8 — 0 4 0 — 0 1 0 — 0 0.25 0 — 0 0.06 0 — 4 4 100 100  1 195 71 0.25 0.25 54 49 0.06 0.06 23  8

Example 16

[0141] Fungicidal efficacy of the mixture of AzolopyrimidineC+quinoxyfen (1 day residual)) against Blumeria graminis on wheat Thetank mix was obtained from technical material of Azolopyrimidine C andquinoxyfen. The observed and expected efficacies with different ratesare given in Table XVI: TABLE XVI dose rate (ppm) Observed ExpectedAzolopyrimidine C quinoxyfen Efficacy Efficacy 4 0 96 — 1 0 42 — 0.25 019 — 0.06 0 0 — 0 4 99 — 0 1 73 — 0 0.25 18 — 0 0.06 8 — 4 4 100 100  11 87 85 0.25 0.25 53 33 0.06 0.06 24  8

Example 17

[0142] Fungicidal efficacy of the mixture of Azolopyrimidine C+metalaxyl(1 day residual) against Blumeria graminis on wheat The tank mix wasobtained from technical material of Azolopyrimidine C and metalaxyl. Theobserved and expected efficacies with different rates are given in TableXVII: TABLE XVII dose rate (ppm) Observed Expected Azolopyrimidine Cmetalaxyl Efficacy Efficacy 4 0 96 — 1 0 42 — 0.25 0 19 — 0.06 0 0 — 0 40 — 0 1 0 — 0 0.25 0 — 0 0.06 0 — 4 4 92 96 1 1 45 42 0.25 0.25 34 190.06 0.06 21  0

Example 18

[0143] Fungicidal efficacy of the mixture of AzolopyrimidineC+famoxadone (1 day residual) against Blumeria graminis on wheat Thetank mix was obtained from technical material of Azolopyrimidine C andfamoxadone. The observed and expected efficacies with different ratesare given in Table XVIII: TABLE XVIII dose rate (ppm) Observed ExpectedAzolopyrimidine C Famoxadone Efficacy Efficacy 4 0 96 — 1 0 42 — 0.25 019 — 0.06 0 0 — 0 4 0 — 0 1 0 — 0 0.25 0 — 0 0.06 0 — 4 4 96 96 1 1 5342 0.25 0.25 34 19 0.06 0.06 9  0

Example 19

[0144] Fungicidal efficacy of the mixture of AzolopyrimidineC+famoxadone (1 day residual) against Puccinia recondita on wheat Thetank mix was obtained from technical material of Azolopyrimidine C andfamoxadone. The observed and expected efficacies with different ratesare given in Table XIX: TABLE XX dose rate (ppm) Observed ExpectedAzolopyrimidine C famoxadone Efficacy Efficacy 4 0 100 — 1 0 71 — 0.25 049 — 0.06 0 8 — 0 4 61 — 0 1 31 — 0 0.25 0 — 0 0.06 0 — 4 4 100 100  1 187 80 0.25 0.25 52 49 0.06 0.06 29  8

Example 20

[0145] Fungicidal efficacy of the mixture of Azolopyrimidine C+dodine (1day residual) against Puccinia recondita on wheat The tank mix wasobtained from technical material of Azolopyrimidine C and a WPcontaining 650 g dodine per kg. The observed and expected Efficacieswith different rates are given in Table XX: TABLE XX dose rate (ppm)Observed Expected Azolopyrimidine C dodine Efficacy Efficacy 0.86 0 8 —0 0.06 0 — 0.06 0.06 28 8

Example 21

[0146] Fungicidal efficacy of the mixture of Azolopyrimidine C+copperoxychloride (1 day residual) against Puccinia recondita on wheat Thetank mix was obtained from technical material of Azolopyrimidine C and aWP containing 450 g copper oxychloride per kg. The observed and expectedefficacies with different rates are given in Table XXI: TABLE XXI doserate (ppm) copper Observed Expected Azolopyrimidine C oxychlorideEfficacy Efficacy 0.06 0 8 — 0 0.06 0 — 0.06 0.06 18 8

Example 22

[0147] Fungicidal efficacy of the mixture of Azolopyrimidine C+sulfur (1day residual) against Puccinia recondita on wheat The tank mix wasobtained from technical material of Azolopyrimidine C and sulfur. Theobserved and expected efficacies with different rates are given in TableXXII: TABLE XXII dose rate (ppm) Observed Expected Azolopyrimidine Csulfur Efficacy Efficacy 1 0 71 — 0 1 0 — 1 1 86 71

Example 23

[0148] Fungicidal efficacy of the mixture of Azolopyrimidine C+triforine(1 day residual) against Erysiphe cichoracearum on cucumbers

[0149] the tank mix was obtained from a SC formulation containing 100 gof Azolopyrimidine C per liter and an DC formulation containing and 190g of triforine per liter. The observed and expected efficacies withdifferent rates are given in Table XXIII: TABLE XXIII dose rate (ppm)Observed Expected Azolopyrimidine C triforine Efficacy Efficacy 4 0 7 —1 0 0 — 0 16 15 — 0 4 0 — 4 16 47 34 1 4 12  0

Example 24

[0150] Fungicidal efficacy of the mixture of AzolopyrimidineC+cyprodinil (1 day residual) against Erysiphe cichoracearum oncucumbers The tank mix was obtained from a SC formulation containing 100g of Azolopyrimidine C per liter and a WG formulation containing and 750g of cyprodinil per kg. The observed and expected efficacies withdifferent rates are given in Table XXIV: TABLE XXIV dose rate (ppm)Observed Expected Azolopyrimidine C cyprodinil Efficacy Efficacy 4 0 7 —1 0 0 — 0 16 29 — 0 4 0 — 4 16 41 34 1 4 10 0

Example 25

[0151] Fungicidal efficacy of the mixture of Azolopyrimidine C anddifferent fungicides (1 day residual) against Alternaria solani ontomatoes The tank mix was obtained from an SC formulation containing 100g Azolopyrimidine A per liter and WP formulations of dithianon (750g/kg), captan (500 g/kg), cyprodinil (750 g/kg), mancozeb (800 g/kg), ora SC formulation of chlorothalonil (500 g/l), or a FS formulation offenpiclonil (400 g/l), spectively. The observed and expected efficacieswith different rates are given in Table XXV: TABLE XXV Azolopyrimidine CCereal rate Observed Expected (g/ha) Fungicide (g/ha) Efficacy Efficacy4 —  0 25 — 0 dithianon 16 50 — 0 captan 16 18 — 0 cyprodinil 16 13 — 0mancozeb 16 27 — 0 chlorothalonil 16 13 — 0 fenpiclonil 16 76 — 4dithianon 16 76 63 4 captan 16 60 38 4 cyprodinil 16 50 35 4 mancozeb 1662 45 4 chlorothalonil 16 57 35 4 fenpiclonil 16 91 82

Example 26

[0152] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Fenhexamid (2 days curative) against Blumeria graminis onbarley. The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Fenhexamid. The active ingredients, theobserved and expected efficacies with different rates are given in TableXXVI: TABLE XXVI dose rate Observed Expected Compound (ppm) EfficacyEfficacy (S)-Azolopyrimidine C 180 86 60 60 20 37 6.7 29 2.2 8 0.74 0Fenhexamid 180 39 60 7 20 1 6.7 0 2.2 0 0.74 0 (S)-Azolopyrimidine C +180 + 180 95 91 Fenhexamid 60 + 60 70 63 20 + 20 42 38 6.7 + 6.7 36 292.2 + 2.2 18 8 0.74 + 0.74 8 0

Example 27

[0153] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Azoxystrobin or Trifloxystrobin (2 days curative) againstBlumeria graminis on wheat. The tank mixes were obtained from technicalmaterial of (S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin.The active ingredients, the observed and expected efficacies withdifferent rates are given in Table XXVII: TABLE XXVII dose rate ObservedExpected Compound (ppm) Efficacy Efficacy (S)-Azolopyrimidine C 50 81 2561 12.5 40 6.3 10 3.1 0 1.6 0 Azoxystrobin 50 61 25 48 12.5 28 6.3 213.1 2 1.6 0 Trifloxystrobin 50 99 25 98 12.5 89 6.3 78 3.1 55 1.6 34(S)-Azolopyrimidine C + 50 + 50 95 93 Azoxystrobin 25 + 25 79 80 12.5 +12.5 62 57 6.3 + 6.3 30 29 3.1 + 3.1 20 2 1.6 + 1.6 14 0(S)-Azolopyrimidine C + 50 + 50 100 100 Trifloxystrobin 25 + 25 100 9912.5 + 12.5 93 93 6.3 + 6.3 75 80 3.1 + 3.1 67 55 1.6 + 1.6 45 34

Example 28

[0154] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Azoxystrobin or Trifloxystrobin (2 days curative) againstPuccinia recondita on wheat. The tank mixes were obtained from technicalmaterial of (S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin.The active ingredients, the observed and expected efficacies withdifferent rates are given in Table XXVIII: TABLE XXVIII dose rateObserved Expected Compound (ppm) Efficacy Efficacy S)-Azolopyrimidine C25 54 12.5 23 6.3 8 3.1 0 1.6 0 Azoxystrobin 25 95 12.5 85 6.3 48 3.1 251.6 0 Trifloxystrobin 25 0 12.5 0 6.3 0 3.1 0 1.6 0 (S)-AzolopyrimidineC + 25 + 25 99 98 Azoxystrobin 12.5 + 12.5 87 88 6.3 + 6.3 81 52 3.1 +3.1 45 25 1.6 + 1.6 18 0 (S)-Azolopyrimidine C + 25 + 25 53 54Trifloxystrobin 12.5 + 12.5 36 23 6.3 + 6.3 15 8 3.1 + 3.1 5 0 1.6 + 1.60 0

Example 29

[0155] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Azoxystrobin or Trifloxystrobin (2 days curative) againstBlumeria graminis on barley. The tank mixes were obtained from technicalmaterial of (S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin.The active ingredients, the observed and expected efficacies withdifferent rates are given in Table XXIX: TABLE XXIX dose rate ObservedExpected Compound (ppm) Efficacy Efficacy (S)-Azolopyrimidine C 50 73 2554 12.5 31 6.3 15 3.1 1 1.6 0 Azoxystrobin 50 87 25 73 12.5 49 6.3 213.1 10 1.6 0 Trifloxystrobin 50 96 25 89 12.5 74 6.3 59 3.1 36 1.6 22(S)-Azolopyrimidine C + 50 + 50 98 96 Azoxystrobin 25 + 25 90 88 12.5 +12.5 75 65 6.3 + 6.3 51 33 3.1 + 3.1 18 11 1.6 + 1.6 1 1(S)-Azotopyrimidine C + 50 + 50 100 99 Trifloxystrobin 25 + 25 98 9512.5 + 12.5 87 82 6.3 + 6.3 61 65 3.1 + 3.1 46 37 1.6 + 1.6 28 22

Example 30

[0156] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Azoxystrobin or Trifloxystrobin (4 days residual) againstBlumeria graminis on wheat. The tank mixes were obtained from technicalmaterial of (S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin.The active ingredients, the observed and expected efficacies withdifferent rates are given in Table XXX: TABLE XXX dose rate ObservedExpected Compound (ppm) Efficacy Efficacy (S)-Azolopyrimidine C 50 34 2511 12.5 3 6.3 0 3.1 0 Azoxystrobin 50 9 25 9 12.5 7 6.3 0 3.1 0Trifloxystrobin 50 14 25 0 12.5 0 6.3 0 3.1 0 (S)-Azolopyrimidine C +50 + 50 49 40 Azoxystrobin 25 + 25 25 19 12.5 + 12.5 18 10 6.3 + 6.3 1 03.1 + 3.1 0 0 (S)-Azolopyrimidine C + 50 + 50 51 43 Trifloxystrobin 25 +25 27 11 12.5 + 12.5 29 3 6.3 + 6.3 7 0 3.1 + 3.1 9 0

Example 31

[0157] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Azoxystrobin or Trifloxystrobin (4 days residual) againstPuccinia recondita on wheat. The tank mixes were obtained from technicalmaterial of (S)-Azolopyrimidine C and Azoxystrobin or Trifloxystrobin.The active ingredients, the observed and expected efficacies withdifferent rates are given in Table XXXI: TABLE XXXI dose rate ObservedExpected Compound (ppm) Efficacy Efficacy (S)-Azolopyrimidine C 50 50 2527 12.5 16 6.3 9 3.1 0 Azoxystrobin 50 8 25 0 12.5 0 6.3 0 3.1 0Trifloxystrobin 50 0 25 0 12.5 0 6.3 0 3.1 0 (S)-Azolopyrimidine C +50 + 50 63 54 Azoxystrobin 25 + 25 28 27 12.5 + 12.5 21 16 6.3 + 6.3 109 3.1 + 3.1 6 0 (S)-Azolopyrimidine C + 50 + 50 59 50 Trifloxystrobin25 + 25 35 27 12.5 + 12.5 15 16 6.3 + 6.3 10 9 3.1 + 3.1 1 0

Example 32

[0158] Fungicidal efficacy of the mixture of (S)-Azolopyrimidine C inadmixture with Azoxystrobin (4 days residual) against Blumeria graminison barley. The tank mixes were obtained from technical material of(S)-Azolopyrimidine C and Azoxystrobin. The active ingredients, theobserved and expected efficacies with different rates are given in TableXXXII: TABLE XXXII dose rate Observed Expected Compound (ppm) EfficacyEfficacy (S)-Azolopyrimidine C 50 28 25 22 12.5 17 6.3 8 3.1 3 1.6 0Azoxystrobin 50 9 25 2 12.5 3 6.3 3 3.1 3 1.6 0 (S)-Azolopyrimidine C +50 + 50 39 34 Azoxystrobin 25 + 25 34 24 12.5 + 12.5 27 19 6.3 + 6.3 2011 3.1 + 3.1 20 6 1.6 + 1.6 14 0

[0159] B Field Tests

Example 33

[0160] Fungicidal efficacy of the mixture of AzolopyrimidineB+pyrimethanil in the field against Botrytis cinerea in vines The tankmix was obtained from a SC formulation containing 100 g ofAzolopyrimidine B per liter and a SC formulation containing 400 g ofpyrimethanil per liter. The observed and expected efficacies are givenin Table XXXIII: TABLE XXXIII dose rate (g/ha) Observed ExpectedAzolopyrimidine B pyrimethanil Efficacy Efficacy 250 0 58 — 0 500 66 —250 500 92 86

Example 34

[0161] Fungicidal efficacy of the mixture of AzolopyrimidineC+metconazole in the field against Septoria tritici on wheat The tankmix was obtained from an EC formulation containing 150 g AzolopyrimidineC per liter and a SL formulation containing 60 g metconazole per liter.The observed and expected efficacies with different rates are given inTable XXXIVa (19 days after application) and Table XXXIVb (25 days afterapplication): TABLE XXXIVa dose rate (g/ha) Observed ExpectedAzolopyrimidine C Metconazole Efficacy Efficacy 25 0 48 — 0 15 9 — 0 3036 — 0 45 24 — 25 15 73 53 25 30 74 67 25 45 76 60

[0162] TABLE XXXIVb dose rate (g/ha) Observed Expected Azolopyrimidine CMetconazole Efficacy Efficacy 50 0 61 — 75 0 13 — 0 15 33 — 0 60 48 — 5015 82 74 75 60 66 55

Example 35

[0163] Fungicidal efficacy of the mixture of (S)-AzolopyrimidineC+kresoxim methyl in the field against Septoria tritici on wheat Thetank mix was obtained from a SC formulation containing 100 g(S)-Azolopyrimidine C per liter and a WG formulation containing 500 gkresoxim methyl per kg. The observed and expected efficacies withdifferent rates are given in Tables XXXVa (7 days after application),XXXVb (22 days after application), XXXVc (34 days after application),and XXXVd (41 days after application): TABLE XXXVa dose rate (g/ha)Observed Expected (S)-Azolopyrimidine C kresoxim methyl EfficacyEfficacy 25 0 34 — 0 100 40 — 25 100 70 60

[0164] TABLE XXXVb dose rate (g/ha) Observed Expected(S)-Azolopyrimidine C kresoxim methyl Efficacy Efficacy 25 0 74 — 100 087 — 0 100 64 — 25 100 92 87 100 100 99 96

[0165] TABLE XXXVc dose rate (g/ha) Observed Expected(S)-Azolopyrimidine C kresoxim methyl Efficacy Efficacy 50 0 53 — 100 070 — 0 50 44 — 0 100 59 — 50 100 88 83 100 50 84 83 100 100 92 88

[0166] TABLE XXXVd dose rate (g/ha) Observed Expected(S)-Azolopyrimidine C kresoxim methyl Efficacy Efficacy 75 0 92 — 0 10092 — 75 100 100 98

Example 36

[0167] Fungicidal efficacy of the mixture of (S)-AzolopyrimidineC+cyproconazole in the field against Blumeria graminis on wheat 17 daysafter application The tank mix was obtained from a SC formulationcontaining 100 g (S)-Azolopyrimidine C per liter and an EC formulationcontaining 60 g cyproconazole per liter. The observed and expectedefficacies with different rates are given in Table XXXVI: TABLE XXXVIdose rate (g/ha) Observed Expected (S)-Azolopyrimidine C cyproconazoleEfficacy Efficacy 25 0 63 — 50 0 78 — 75 0 74 — 0 15 86 — 0 30 82 — 2515 96 95 25 30 98 93 50 30 100 96 75 30 98 95

Example 37

[0168] Fungicidal efficacy of the mixture of (S)-AzolopyrimidineC+azoxystrobin in the field against Blumeria graminis on wheat 17 daysafter application The tank mix was obtained from a SC formulationcontaining 100 g (S)-Azolopyrimidine C per liter and a SC formulationcontaining 250 g azoxystrobin per kg. The observed and expectedefficacies with different rates are given in Table XXXVII: TABLE XXXVIIdose rate (g/ha) Observed Expected (S)-Azolopyrimidine C AzoxystrobinEfficacy Efficacy 25 0 63 — 50 0 78 — 75 0 74 — 100 0 96 — 0 75 49 — 2575 92 81 50 75 94 89 75 75 92 86 100 75 100 98

Example 38

[0169] Fungicidal efficacy of the mixture of Azolopyrimidine A anddifferent cereal fungicides in the field against Blumeria graminis onwheat 15 days after application The tank mix was obtained from an SCformulation containing 100 g Azolopyrimidine A per liter andcommercially available formulations of metconazole, epoxiconazole orkresoxim methyl, respectively. The observed and expected efficacies withdifferent rates are given in Table XXXVIII: TABLE XXXVIII Cereal rateObserved Expected Azolopyrimidine A Fungicide (g/ha) Efficacy Efficacy125 — 0 22 — 0 metconazole 45 54 — 0 epoxiconazole 63 40 — 0 kresoximmethyl 100 85 — 125 metconazole 45 79 64 125 epoxiconazole 63 74 53 125kresoxim methyl 100 92 88

Example 39

[0170] Fungicidal efficacy of the mixture of Azolopyrimidine A anddifferent cereal fungicides the field against Septoria tritici on wheat15 days after application The tank mix was obtained from an SCformulation containing 100 g Azolopyrimidine A per liter andcommercially available formulations of metconazole, epoxiconazole orpropiconazole, respectively. The observed and expected efficacies withdifferent rates are given in Table XXXIX: TABLE XXXIX Cereal rateObserved Expected Azolopyrimidine A Fungicide (g/ha) Efficacy Efficacy125 —  0 63 — 0 metconazole 45 77 — 0 epoxiconazole 63 93 — 0propiconazole 63 72 — 125 metconazole 45 99 91 125 epoxiconazole 63 9797 125 propiconazole 63 93 90

Example 40

[0171] Fungicidal efficacy of the mixture of Azolopyrimidine A anddifferent cereal fungicides in the field against Puccinia recondita onwheat 50 days after application The tank mix was obtained from an SCformulation containing 100 g Azolopyrimidine A per liter andcommercially available formulations of metconazole, epoxiconazole,propiconazole or kresoxim methyl, respectively. The observed andexpected efficacies with different rates are given in Table XXXX: TABLEXXXX Cereal rate Observed Expected Azolopyrimidine A Fungicide (g/ha)Efficacy Efficacy 125 — 0 0 — 0 metconazole 45 75 — 0 epoxiconazole 6395 — 0 propiconazole 63 49 — 0 kresoxim methyl 100 0 — 125 metconazole45 85 75 125 epoxiconazole 63 97 95 125 propiconazole 63 67 49 125kresoxim methyl 100 64 0

What is claimed is:
 1. A fungicidal composition comprising afungicidally acceptable carrier and/or surface active agent andsynergistically effective amounts of (a) at least one azolopyrimidine offormula I

 in which R¹ represents a C₁₋₆ alkyl, C₃₋₆ alkenyl or C₁₋₆ haloalkylgroup, and R² represents a hydrogen atom or a C₁₋₆ alkyl group, or R¹and R² taken together represent a C₃₋₈ alkylene group; L¹ represents ahalogen atom; and L² and L³ each independently represent a hydrogen or ahalogen atom; and (b) at least one fungicidal active ingredient selectedfrom the following groups (A), (B) and (C): (A) a compound selected fromthe group consisting of benomyl, carboxin, captan, chlorothalonil,copper oxychloride, cyprodinil, dimethomorph, dithianon, dodine,famoxadone, fenhexamid, fenpiclonil, fenpropimorph, fluazinam, mancozeb,metalaxyl, pyrimethanil, quinoxifen, sulfur, triforine and vinclozolin;(B) a fungicidal triazole derivative; and (C) a synthetic strobilurinederivative.
 2. A composition as claimed in claim 1, wherein the triazolederivative (B) is selected from the group consisting of cyproconazole,epoxiconazole, metconazole, propiconazole and tebuconazole.
 3. Acomposition as claimed in claim 1, wherein the synthetic strobilurinederivative is a compound of formula III,

wherein A represents N or CH; B represents a —O—, —OCH₂—, a —CH₂O—, apyrimid-4,6-dioxydiyl group or a group of formula

R³ represents a C₁₋₄ alkyl group; R⁴ represents a C₁₋₆ alkoxy or a C₁₋₆alkylamino group; R⁵ represents a hydrogen or halogen atom or a cyano, aC₁₋₄ alkyl or a C₁₋₄ haloalkyl group; and m 0, 1 or
 2. 4. A compositionas claimed in claim 1 wherein in the compound of formula I


5. A composition as claimed in claim 4, wherein the azolopyrimidine isselected from the group consisting of:5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperid-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine,5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2,2,2-trifluoroethylamino)-[1,2,4]triazolo[1,5-a]pyrimidine,and5-chloro-6-(2,4,6-trifluorophenyl)-7-(1,1,1-trifluoroprop-2-ylamino)-[1,2,4]triazolo[1,5-a]pyrimidine.6. A composition as claimed in claim 3, wherein the strobilurinederivative is selected from azoxystrobin, trifloxystrobin and kresoximmethyl.
 7. A composition as claimed in claim 1, wherein the ratio (byweight) of the fungicidal compound (b) to the azolopyrimidine of formulaI (a) is approximately from 0.01:1 to 100:1.
 8. A method of controllingthe growth of phytopathogenic fungi at a locus which comprises applyingsynergistically effective amounts of (a) at least one azolopyrimidine offormula I as defined in claim 1 and (b) at least one at least onefungicidal active ingredient as defined in claim 1, to the locus.
 9. Amethod of controlling wheat leaf rust, wheat Septoria leaf blotch and/orwheat powdery mildew which comprises applying synergistically effectiveamounts of at least one azolopyrimidine of formula I and at least one atleast one fungicidal active ingredient selected from the groups (A), (B)and (C), as defined in claim 1 to the locus.
 10. A fungicidalcomposition comprising a fungicidally acceptable carrier and/or surfaceactive agent and synergistically effective amounts of (c) at least oneazolopyrimidine of formula I

 in which R¹ represents a C₁₋₆ alkyl, C₃₋₆ alkenyl or C₁₋₆ haloalkylgroup, and R² represents a hydrogen atom or a C₁₋₆ alkyl group, or R¹and R² taken together represent a C₃₋₈ alkylene group; L¹ represents ahalogen atom; and L² and L³ each independently represent a hydrogen or ahalogen atom; and (d) at least one fungicidal active ingredient selectedfrom the following groups (A), (B) and (C): (A) a compound selected fromthe group consisting of benomyl, carboxin, captan, chlorothalonil,copper oxychloride, cyprodinil, dimethomorph, dithianon, dodine,famoxadone, fenpiclonil, fenpropimorph, fluazinam, mancozeb, metalaxyl,pyrimethanil, quinoxifen, sulfur, triforine and vinclozolin; (B) afungicidal triazole derivative; and (C) a synthetic strobilurinederivative.
 11. A composition as claimed in claim 10 wherein in thecompound of formula I


12. A composition as claimed in claim 11, wherein the azolopyrimidine isselected from the group consisting of:5-chloro-6-(2-chloro-6-fluorophenyl)-7-(4-methylpiperid-1-yl)-[1,2,4]triazolo[1,5-a]pyrimidine,5-chloro-6-(2-chloro-6-fluorophenyl)-7-(2,2,2-trifluoroethylamino)-[1,2,4]triazolo[1,5-a]pyrimidine,and5-chloro-6-(2,4,6-trifluorophenyl)-7-(1,1,1-trifluoroprop-2-ylamino)-[1,2,4]triazolo[1,5-a]pyrimidine.13. A composition as claimed in claim 10, wherein the ratio (by weight)of the fungicidal compound (b) to the azolopyrimidine of formula I (a)is approximately from 0.01:1 to 100:1.
 14. A method of controlling thegrowth of phytopathogenic fungi at a locus which comprises applyingsynergistically effective amounts of (a) at least one azolopyrimidine offormula I as defined in claim 10 and (b) at least one at least onefungicidal active ingredient as defined in claim 10, to the locus.